Platinum–thallium cluster complexes

Abstract

The synthesis of new Pt3Tl complexes [Pt3{μ3-Tl(diketonate)(OH2)}(μ3-CO)(μ-dppm)3][PF6]2, 2, dppm = Ph2CH2PPh2, by reversible addition of thallium(I) β-diketonates to the complex cation [Pt3(μ3-CO)(μ-dppm)3]2+, is reported. The thallium(I) units are easily displaced from platinum by halide ions X− (X = Cl, Br, I) to give [Pt3(μ3-CO)(μ3-X)(μ-dppm)3]+, or by SnCl3− to give [Pt3(μ3-CO)(μ3-SnCl3)(μ-dppm)3]+. With trifluoroacetate there was an equilibrium with [Pt3(μ3-CO)(μ3-O2CCF3)(μ-dppm)3]+ and [Pt3{μ3-Tl(diketonate)(O2CCF3)}(μ3-CO)(μ-dppm)3]+. The structures of two Pt3Tl clusters are reported, and the Pt3Tl unit is shown to be tetrahedral.